Yu-Cheng Huang

Filling the oxygen vacancies in Co3O4 with phosphorus: an ultra-efficient electrocatalyst for overall water splitting

It is of essential importance to design an electrocatalyst with excellent performance for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in water splitting. Co3O4 has been developed as a highly efficient OER electrocatalyst, but it has almost no activity for HER. In a previous study, it has been demonstrated that the formation of oxygen vacancies (VO) in Co3O4 can significantly enhance the OER activity. However, the stability of VO needs to be considered, especially under the highly oxidizing conditions of the OER process. It is a big challenge to stabilize the VO in Co3O4 while reserving the excellent activity. Filling the oxygen vacancies with heteroatoms in the VO-rich Co3O4 may be a smart strategy to stabilize the VO by compensating the coordination numbers and obtain an even surprising activity due to the modification of electronic properties by heteroatoms. Herein, we successfully transformed VO-rich Co3O4 into an HER-OER electrocatalyst by filling the in situ formed VO in Co3O4 with phosphorus (P-Co3O4) by treating Co3O4 with Ar plasma in the presence of a P precursor. The relatively lower coordination numbers in VO-Co3O4 than those in pristine Co3O4 were evidenced by X-ray adsorption spectroscopy, indicating that the oxygen vacancies were created after Ar plasma etching. On the other hand, the relatively higher coordination numbers in P-Co3O4 than those in VO-Co3O4 and nearly same coordination number as that in pristine Co3O4 strongly suggest the efficient filling of P in the vacancies by treatment with Ar plasma in the presence of a P precursor. The Co–O bonds in Co3O4 consist of octahedral Co3+(Oh)–O and tetrahedral Co2+(Td)–O (Oh, octahedral coordination by six oxygen atoms and Td, tetrahedral coordination by four oxygen atoms). More Co3+(Oh)–O are broken when oxygen vacancies are formed in VO-Co3O4, and more electrons enter the octahedral Co 3d orbital than those entering the tetrahedral Co 3d orbital. Then, with the filling of P in the vacancy site, electrons are transferred out of the Co 3d states, and more Co2+(Td) than Co3+(Oh) are left in P-Co3O4. These results suggest that the favored catalytic ability of P-Co3O4 is dominated by the Co2+(Td) site. P-Co3O4 shows superior electrocatalytic activities for HER and OER (among the best non-precious metal catalysts). Owing to its superior efficiency, P-Co3O4 can directly catalyze overall water splitting with excellent performance. The theoretical calculations illustrated that the improved electrical conductivity and intermediate binding by P-filling contributed significantly to the enhanced HER and OER activity of Co3O4.

Molecular Design of Polymer Heterojunctions for Efficient Solar–Hydrogen Conversion

Semiconducting photocatalytic solar-hydrogen conversion (SHC) from water is a great challenge for renewable fuel production. Organic semiconductors hold great promise for SHC in an economical and environmentally benign manner. However, organic semiconductors available for SHC are scarce and less efficient than most inorganic ones, largely due to their intrinsic Frenkel excitons with high binding energy. In this study the authors report polymer heterojunction (PHJ) photocatalysts consisting of polyfluorene family polymers and graphitic carbon nitride (g-C3 N4 ) for efficient SHC. A molecular design strategy is executed to further promote the exciton dissociation or light harvesting ability of these PHJs via alternative approaches. It is revealed that copolymerizing electron-donating carbazole unit into the poly(9,9-dioctylfluorene) backbone promotes exciton dissociation within the poly(N-decanyl-2,7-carbazole-alt-9,9-dioctylfluorene) (PCzF)/g-C3 N4 PHJ, achieving an enhanced apparent quantum yield (AQY) of 27% at 440 nm over PCzF/g-C3 N4 . Alternatively, copolymerizing electron-accepting benzothiadiazole unit extended the visible light response of the obtained poly(9,9-dioctylfluorene-alt-benzothiadiazole)/g-C3 N4 PHJ, leading to an AQY of 13% at 500 nm. The present study highlights that constructing PHJs and adapting a rational molecular design of PHJs are effective strategies to exploit more of the potential of organic semiconductors for efficient solar energy conversion.

Engineering the coordination geometry of metal–organic complex electrocatalysts for highly enhanced oxygen evolution reaction

Designing highly efficient oxygen evolution reaction (OER) electrocatalysts is very important for various electrochemical devices. In this work, for the first time, we have successfully generated coordinatively unsaturated metal sites (CUMSs) in phytic acid–Co2+ (Phy–Co2+) based metal–organic complexes by engineering the coordination geometry with room-temperature plasma technology. The CUMSs can serve as active centers to catalyze the OER. The electron spin resonance and X-ray absorption spectra provide direct evidence that the coordination geometry is obviously modified with many CUMSs by the plasma treatment. The plasma treated Phy–Co2+ (P-Phy–Co2+) only requires an overpotential of 306 mV to reach 10 mA cm−2 on glassy carbon electrodes. When we expand this strategy to a CoFe bimetallic system, it only needs an overpotential of 265 mV to achieve 10 mA cm−2 with a small Tafel slope of 36.51 mV dec−1. P-Phy–Co2+ is superior to the state-of-the-art. Our findings not only provide alternative excellent OER electrocatalysts, but also introduce a promising principle to design advanced electrocatalysts by creating more CUMSs.

Visible light-induced electronic structure modulation of Nb- and Ta-doped α-Fe2O3 nanorods for effective photoelectrochemical water splitting

The photoelectrochemical (PEC) water splitting activity of Nb and Ta-doped hematite (α-Fe2O3) nanorods was investigated with reference to electronic structures by in situ synchrotron x-ray absorption spectroscopy (XAS). Current density-potential measurements demonstrate that the PEC activity of α-Fe2O3 nanorods depends strongly on the species and concentrations of dopants. The doping of α-Fe2O3 nanorods with a low level of Nb or Ta can improve their electrical conductivity and thereby facilitate charge transport and reduced electron-hole recombination therein. The photoconversion effects of Nb and Ta-doped α-Fe2O3 by in situ XAS in the dark and under illumination revealed opposite evolutions of the spectral intensities of the Fe L-edge and Nb/Ta L-edge, indicating that charge transfer and a conduction pathway are involved in the photoconversion. Analytic in situ XAS results reveal that the α-Fe2O3 that is doped with a low level of Nb has a greater photoconversion efficiency than that doped with Ta because Nb sites are more active than Ta sites in α-Fe2O3. The correlation between PEC activity and the electronic structure of Nb/Ta-doped α-Fe2O3 is examined in detail using in situ XAS and helps to elucidate the mechanism of PEC water splitting in terms of the electronic structure.

Electronic Structure Evolution in Tricomponent Metal Phosphides with Reduced Activation Energy for Efficient Electrocatalytic Oxygen Evolution

Non-noble metal catalysts for high-active electrocatalytic oxygen evolution reaction (OER) are essential in large-scale application for water splitting. Herein, tricomponent metal phosphides with hollow structures are synthesized from cobalt-contained metal organic frameworks (MOFs), i.e., ZIF-67, by tailoring the feeding ratios of Ni and Fe, followed by a high-temperature reduction and a subsequent phosphidation process. Excellent OER activity and long-time stability are achieved in 1 m NaOH aqueous solution, with an overpotential of 329 mV at 10 mA cm-2 and Tafel slope of 48.2 mV dec-1 , even superior to the noble metal-based catalyst. It is evidenced that the formed (oxyhydr)oxide/phosphate species by in situ electrochemical surface oxidation are responsible for active OER. Accordingly, the simultaneous introduction of external Ni and Fe elements significantly influences the electronic structures of the parent metal phosphides, leading to the in situ electrochemical formation of surface active layer with decreased OER activation energy for greatly improved water oxidation performance. This electronic structure tuning strategy by introducing multicomponent metals demonstrates a versatile method to use MOFs as precursors for synthesizing high-efficient water splitting electrocatalysts.